April, 1928 INDUSTRIAL AND ENGINEERING CHEMISTRY
distillations this difference is negligible. If any distillate
enters the manometer it will enter the large chamber, and
will not interfere with the reading of the column.
No stopcock is necessary in connecting the manometer
to a system. It can be connected directly by attaching a
rubber hose to the tapered tube, which is bent a t a right
angle. The absence of a stopcock makes the manometer
Solubility of Paraffin W a x in Pure Hydrocarbons'
Paul Weber and H. L. Dunlap
SCHOOL OF
ERY few data are available in the literature on the
V solubility of solid paraffins in the liquid hydrocarbons
of lower molecular weight. Sakhanov and Vasil'ev2
determined the solubility of solid paraffins and the solidi-
fying temperatures of materials containing them. The sol-
vents used were liquid paraffins, benzene, machine oil, and
acetic acid. They found that the solubilities increased rather
rapidly with rise of temperature. For any particular sol-
vent the solubility is greater the lower the melting point of
the paraffin, and for any paraffin the solubility decreases
wit'h the increasing density of the solvent. Sakhanov3
determined the solubilit'y of paraffin in various gasolines,
kerosene, solar oil, paraffin oil, fuel oil, benzene, alcohol,
and acetic acid.
Sullivan, McGill, and French4 determined the solubility
of closely fractionated paraffin wax of various petroleum
fract'ions. The following conclusions were drawn from this
work:
1-The solubility of paraffin waxes increases as the melting
point of the wax decreases.
2-The solubility of paraffin waxes in petroleum oil decreases
with increasing viscosity of solvent.
3-Differences in solubility due to differences in the melting
point of the wax, or to variations in the viscosity of the solvent,
decrease with decreasing temperature.
The present authors determined the solubility of a fairly
pure paraffin in the pure lower molecular-weight hydro-
carbons in order to find out if any relationship existed be-
tween the decreasing solubility and the increased molecular
weight of the solvent hydrocarbon.
Preparation and Purification of Solid and Liquid Alkanes
SOLID PARAFFIX-The solid hydrocarbon was obtained
from a sample of refined paraffin by careful recrystallization
three times from benzene, the sample used being about 25
per cent of the original amount. That part which first
crystallized from the benzene was taken for the next recrys-
tallization each time. The last traces of benzene were re-
moved by distillation under reduced pressure with a fine
stream of air bubbling through the molten paraffin. This
product undoubtedly contains several constituents, but as
no purer products could be obtained, it was used for the com-
parative figures. The melting point of the paraffin was
56" C., and the density 0.775 a t 20"/4" C.
LIQUIDHYDROCARBOKS-The liquid hydrocarbons were
n-pent,ane, n-hexane, n-heptane, n-octane, and isodecane.
The pentane was secured by a careful fractionation of natural
gasoline. The heptane was obtained from the Eastman
1 Received November 4, 1927.
2 X e f f y a n o e Khozyaisfuo, 6, 820 (1924).
* Petroleum, Z.,21, 735 (1926).
4 Ind. Eng. Cliem., 19, 1042 (1927).
383
very inexpensive. Including the labor of construction and
the price of the glass tubing and mercury, the cost
of the apparatus does not exceed $2.00. For this reason
it is possible to use it in classes of general organic chemistry
as well as by research workers in industrial and educational
institutions. The glass blowing was done by E. F. Grienke
of this university.
MINESA N D METALLURGY,
ROLLA,M O .
Kodak Company and refractioned. The others were pre-
pared from alcohols using methods for synthesis suggested by
the Eastman Kodak Company-namely, the Wiirtz reaction.
These hydrocarbons, after treatment with cold sulfuric acid,
washing with sodium carbonate solution, drying over metallic
sodium and the final distillation, gave the constants indicated
in Table I as compared with those given in the International
Critical Tables.
Table I-Constants of Liquid Hydrocarbons
BOILINGPOINT SPECIFIC GRAVITY
HYDROCARBON Found I. C. T. (2Oo/4O C.)
0 c. OC. Found I.C.T.
+Pentane 36.1-36.3 36.2 0.631 0.631
n-Hexane 68.9-69.2 69.0 0.661 0.660
n-Heptane 98.2-98.4 98.4 0.684 0.684
n-Octane 124.5-124.6 124.6 0.706" 0.707"
Isodecane 159.8-160.1 160.0 0.721 0.722
a Temperature 15'/4' C.
Solubility Determinations
APPARATUS-Ade Khotinsky thermostat with which tem-
perature could be regulated to one-tenth of a degree was
used for the bath. By using a strong salt solution and plac-
ing the thermostat in a cold room, the lower temperatures
were easily maintained. Receptacles for the solutions con-
sisted of ground-glass-stoppered wash bottles to which con-
densers had been sealede6 These flasks, with their condensers,
were attached to a frame, which was rotated almost a quarter
turn in the bath by an arm attached to a motor-driven wheel.
PROCEDURE-ApprOXimately 200 cc. of solvent were placed
in the flask and then solid paraffin was added until a slight
excess remained undissolved at the temperature at which
the solubility was to be determined. At least 5 hours were
allowed for equilibrium to be reached before the first sample
was taken. The flasks were then raised out of the bath,
warmed to dissolve some of the excess paraffin, replaced in
the thermostat, and the second sample taken after a mini-
mum of 5 hours. All determinations were discarded that
did not check within 0.1 per cent. The samples were placed
in 50-cc. glass-stoppered weighing bottles to eliminate loss
of solvent by evaporation before weighing. The solvents
were then evaporated in a closed vessel (reduced pressure
for isodecane) until the paraffin residue gave a constant
weight.
This method was used for each of the solvents with known
weights of paraffin, and the exact procedures in which the
paraffin could be recovered were used for the unknown sam-
ples. The melting points of the paraffin residues checked
the original melting points within 1" C.
EXPERIMENTAL DATA-The solubility of the solid paraffi
in the liquid hydrocarbons is calculated and recorded as
5 Weber and Dunlap, Ind. Eng. Chem., 19, 481 (1927).
384 INDUSTRIAL AND ENGINEERING CHEMISTRY VOl. 20, No. 4
grams paraffin per 100 cc. solvent and also as grams solid Table 11-Solubility Data-Grams Paraffin per 100 cc. Solvent
paraffin per mol of solvent. (Tables I1 and 111) Data TEMPERA-PEN- HEX- HEP- Oc- Iso-
TURE TANE ANE TANE TANE DECANE
for solubilities are given to two decimal places only. The 0 (1.

relation between solubility and carbon content of the solvent 0 2.77 1.37 0.99 ...
5 ... 3.69 2.18 1.69 0.94
is shown in Figure 1. Slight variations in the amounts of ex- 10 5.11 4.81 3.55 2.90 1.44
15 6.94 6.07 5.06 4.24 2.74
cess solid paraffin in the flask alter the solubility data. Thus 20 9.53 8.31 7.18 5.93 4.9s
the figures given may be considered as fairly close for the 25 17.16 16.23 14.36 11.66 9.17
paraffin used. More exact data could be obtained only by Table 111-Solubility Data-Grams Paraffin per Mol Solvent
the use of a solid paraffin which contained only one indi- TEMPERA- PEN- HEX- HEP- OC- Iso-
TURE TANE ANE TANE TANE DECANE
vidual hydrocarbon. The relative solubilities for a pure par- c.
affin in these solvents would undoubtedly be in the same order 0 ... 3.61 2.01 1.60 ...
as that found in this work. 5 ... 4.81 3.22 2.73 1.84
10 5.83 6.28 5.23 4.67 2.84
15 7.92 7.91 7.48 6.84 5.40
20 10.87 10.83 10.57 9.58 9.80
25 19.48 21.33 21.06 18.81 18.03

Summary of Data
The solubility of a solid paraffin in hydrocarbons of low
molecular weight increases rapidly with rise of temperature.
The solubility increases from that of isodecane to that of
pentane. The increase in solubility with rise of temperature
is more rapid with the higher molecular-weight solvent.
This can be seen by dividing the solubilities a t 10" C. into
the solubility a t 25" C., the ratio being 2.3, 3.8, 4.0, 3.9, and
6.6, respectively, for pentane, hexane, heptane, octane, and
isodecane;
I n Table 111, except for the first three sets of data for
octane and isodecane, the data run fairly constant. This
indicates that the mol ratios of solvents to solute may be
constant, and that we have in each case a definite number
of molecules of solvent associated with a molecule of solute.

Some Azo Dyes Soluble in Non-Aqueous Solvents'

Clarence E. May and Herschel Hunt
INDIANA BLOOMINOTON,IND.
UNIVERSITY,

IL-SOLUBLE dyes have been used for years in color- aniline in 200 cc. HzO containing enough HCl to show a

0 ing fancy candles, oleomargarine, floor wax, shoe

polish, ethyl gasoline, and plates for radio photog-
raphy. One outstanding oil-soluble dye is the antiseptic
oil scarlet used in medicine. This dye is used either as an
ointment, a solution of the dye in paraffin, or a solution of
the sulfonic acid derivative in water as an antiseptic and an
aid in the promotion of granulation in wounds that do not
heal readily.
The authors have made and studied a number of dyes
which they have been unable to find in the literature. Each
new dye has been given a short name which has been selected
on account of the color, the relation of the dye to some other
dye, or some other point of interest. This work included the
study of thirty dyes each of which was soluble in non-aqueous
solvents. None of the dyes showed an appreciable solubility
in water.
Table I shows the dyes made, the intermediates used,
and the melting points of the dyes.
Preparation of Dyes
ANILIXEYELLOWG(C1gH1,N8)-A solution of 10 grams
of 2-naphthylamine in 20 grams of c. P. HCl and 200 cc.
HzO was made, cooled and diazotized to the point where, on
the addition of a dilute NaONO solution, a permanent pale
blue color remained on the KI-starch paper. The diazo
solution was then poured into a solution of 9 grams of dimethyl-
1 Received November 19, 1927.
free mineral acidity in the mixture. After standing a few
hours, sufficient sodium acetate was added to destroy the
free mineral acidity. There resulted 11 grams of greenish
yellow substance showing the following analysis:
0.2000 gram substance gave 0.5770 gram COZ and 0.0930
gram HzO
Found: C = 78.68%; H = 5.48%. Theory: C = 78.54%;
H = 5.18%
Azo COCCINERR(ClgHl~NzO)-Commercial xylidine (5
grams) was dissolved in 20 grams c. P. HC1 and 200 cc. HzO
cooled to 15" C. This solution was diazotized in the usual
way and poured into a solution of 6 grams 1-naphthol in 18
grams NaOH and 300 cc. HzO. After standing a day, 8.0
grams of dark red powder, showing the following analysis,
resulted :
0.2027 gram substance gave 0.5810 gram COZand 0.1047 gram
H2O
Found: C = 78.16%; H = 5.81%;. Theory: C = 78.26%;
H = 5.597'30
BENZIDINEBRom(C2~H20N402)-Thetetrazotization of
5 grams benzidine in 200 cc. H 2 0 and 30 grams c. P. HC1
was carried out a t 10" C. The tetrazo solution was poured
into a solution of 4 grams 1-naphthol, 2.4 grams phenol, and
20 grams NaOH in 200 cc. HzO. After standing, 8 grams of
black powder, showing the following analysis, were obtained:
0.2089 gram substance gave 0.5784 gram COn and 0.0851 gram
Ha0